Alhdycuc gtjanamines



desired `hydrophobic properties.

Patented June 24, 1947 U NIT ED STATES PAT ENT O FFI CE ALCYCLIC GUANAMINES Jack Theo Thurston, Cos Cob, Conn., assigner to A liierican Cyana'in'id Company, New York',

N. Y., a corporation of Maine Nro-Drawing.. .Application August 30, 1941, Serial No'. 409,146

Y 1 This invention relatesto alicycl'ic-guanamines, that :is: tosay, guaina-mines in which the 2`carbon atomfof therilG-diami-no-'l -triazine ring is substitute'd by an alicycl-ic radical through a carbonto-carbon bond. The invention also -includes-:i proved methods of preparing such compounds.

Guanamines have obtained considerable practical importance `for the Vproduction of resins by reacting with formaldehyde. In order to have resins which before curing are organo-soluble and which haveY desirable properties for textile nishes, it has been 'found to be desirable to have a substituent on the 2-carbon atoms of the triazine ring which is aliphatic' in nature and which is of suflicient molecular weight to confer the Preferably the radicalv shouldcontain morerthan seven carbon atoms: and those containinga stili larger number of carbon atoms are preferred. Alicyclic guanamines can be `prepared from fairly cheap raw materialsand are obtainable in good yields particuiarly when a strongly basic condensing agent suchas a metal VVa-l-lroxide is used.

Among the alicycl-ic guanam-ines which can be produced according vto the present invention are -thosetrorn2 esters of hexahyd-rcbenzoic` acid, cyclo.-

-hexylacetic acid,` cycling)entyilaceticv acid` and similar monocyclic acids` `mothervvide range oi alicyclic guanamines are those from the tetrahydrophthalic acid group `which are adducts of maleicf anhydride andvarious unsaturated `cornpounds suoh as butadiene, phellandrene, cyclopentadiene, allocimene, .dehydrated castor oil containing conjugated octadecadiene groups, isomerized linseed and soya bean oils whichv like- Wise- Afori-nV diem'c compounds with conjugated double bond'sy andthe like. Adducts with maleic anhydride and dienes which are not conjugated are also' included such as the adductsifrom'maleic a-nhycgiridev and. 9,1-2-linoleic acid esters, dipentene, and soiorth. -Many of theadducts are not` symmetrical and `therefore. isomeric guanamin'es can bel obtained depending uponthemanner iin-,which the anhydride isvopened during half esterification.

Thermos/t v important-products of. the` present invention `are: the onesl prepared from biguanide itself. these products theA amino'rgroups Vof theI triazinering are-unsubstitutedfand the prod- .uctscangbe prepared' with` best yieldsandlsifmpl'est procedures. However, .thef present invention.. also includes,V `products prepemad"` from Asubstituted biguanides such. V.as phenyl bguanide, allyl biguanide or dimethyl biguanidewinwhich. case the correspondingly substituted guanaminesf are obtained. Whernsubstituted biguanides aroused ini place fcrbiguanidaftne,reaction `does 4noti/inrothe y aleenone group inA trie ester aumen-rs;tuA pray ,but lttlieisart rn the' effectiveness of' the' reacties.

Thus', While it i`s` possible' to' usee'sters di `polyhy'dric' .alcohols such asfgl'ycerirfe, glycine, theiiike, I prefer' toi useiesters or monomeric-alee- 'l`iol's and have fou'rld 'that the' lower' members sueltas' methyl-.and ethyl esters are yvery ene-cuve n W,generall the preferred procz'es's-oil the present invention operatesfbest in` thepreseneeholf' a suitable solvent jfor" tl're biguanide and/'or the ester.

'Il haveY foune that the-limer molecular' weight aieonoisare .particularly effective as-tiieye-regeed solvents forbigdanide. The cheap monolydilfc 'params aleenorsL suches metharrer anziV ethanol operare wei-1- ena are of particular advantage-tie'- eaus'e' the most `readilyaveilable esterser "the carboxylic" acids -are usually the" methyl andi ethyl esters, and if the" aicoiiol W-'lliclr-fisT used aisy a solvent corresponds tdytl'ieY a'flcohol radical of the ester,` no `separation. problemy arises. Excellent results are, however,. obtained' with the lower monohydric alcohols such as ether alcohols, forexample,the ethyl ether of ethylene glycol.

The invention will be described greater detail in conjunction with the following specific examples.

Example f Naphthenoganamiie A mixture of naphthenic acids having a neutral equivalent of 239 were esteried with butanol forming the butyl ester and condensed with eq'uinfrole'cularl proportione- .of lciguanideI ,and sodium methylate': -'sy-rupy liquid was obtained which on treatment. with sulfuric acid and chloroform precipitated theY sulfate salt of the naphthenoguanamine. It was filtered, Washed with chloroform and dried. The salt was then dispersed in Water and antoxcess'lof alkali added to form the free base which was then dissolved in methanol, decolorized with charcoal and precipitated by addingwater'. A 30% yield was obtained of a product melting between 64--76l C.

Example 2 2carboxy-3-methy1-6-isopropyl endoethylene tetrahydro bcnzoguanamine CHa CH! (Il /NHQ /C\ /N-C\ Ho (im oH-o )N 1 2 N=o H2 H H-COOH NH2 and 2-carboxy-3-isopropyl-6-methyl endoethylene tetrahydro henzoguan amine CH; /NHg /N C\ Ho (LH Cia-o )N l .Hl N=o\ H H-oooH NH,

| Us Ca CH;

A methanol solution containing 102 parts of 3-methyl 6 isopropylendoethylene tetrahydrophthalic anhydride was refluxed for four hours and then slowly neutralized with parts of sod ium dissolved in methanol. Precipitation of the sodium salt was avoidedl by the addition of 300 parts of the ethyl ether of ethylene glycol. To the reaction mixture was then added 51 parts of biguanide which was stirred until it dissolved and the mixture was then allowed to stand at room temperature for a considerable period of time until reaction appeared to be substantially complete. The methanol was then evaporated and the product dissolved in water, acidiiied with dilute sulfuric acid andextracted three times with carbon tetrachloride. The guanamine in the form of its sulfate was immiscible both with Water and with carbon tetrachloride and was neutralized with ammonium hydroxide, the free base being precipitated from solution as a line white. powder which after several washings With water gave a product melting at 22S-226 C. The yield was approximately 40%.

Example 3 Z-carboxy-- (w-carb omethoxy-a-n-nonenyl)--n-butyltetrahy drobenzoguanamlne CH=CH v y CH3(CH2)3C C11-CH 305 parts of a methyl a and ,B eleostearatemalec anhydride adducts prepared by condensing the methyl ester of tung oil acids with maleic anhydride by the Diels-Alder reaction was reiiuxed for three to four hours with 403 parts of methanol. The free acid Was then converted to A.the sodium salt by slowly adding 15.4 parts of dissolved sodium in methanol with vigorous stirring. 70 parts of biguanide were added and the mixture allowed to stand at room temperature until reaction appeared complete. The solution darkened somewhat on the addition of the biguanide. The guanamine was isolated by recovering the methanol by evaporation and acidifying a water solution of the product with hydrochloric acid. After extracting severaltimes with carbon tetrachloride, the guanamine salt which formed an immiscible layer, was neutralized with ammonium hydroxide and the insoluble product washed three times with water and dried. The guanamine was obtained as a light brown brittle product which softens from 'l0-95 C., the yield'being about 64% Example 4 o-carboxy-endomethylene-tetrahydrobenzoguanamine Fifty parts of biguanide were added to 109 parts of sodium methyl endomethylene-tetrahydrobenzoate dissolved in 300 parts of methanol. This reaction mixture Was stirred for about 24 hours and then ltered. The insoluble sodium salt was washed with about 200 parts of methanol and the combined methanol ltrates evaporated to yield more product. The sodium salt Was dissolved in 300 parts of water and acidied to a pH of about 4.0 in order to precipitate the ocarboxy endomethylene tetrahydrobenzoguan- Thirty-one parts of distilled dimerized methyl esters of soy bean oil prepared as given in Industrial Engineering Chemistry 32, 806 (1940) and 33, 86 (1941) was added to a solution of 10 parts of biguanide in parts of methanol and 90 parts of ethanol. After standing for about a day, a small amount of an insoluble material was removed by filtration and the filtrate was evaporated. The residue was extracted with 600 parts of acetone which yielded 16 parts of a crystalline product that was recrystallized from ethylA acetate. After thoroughly drying the colorless product melted at 'l5-78 C. and was identified as a guanamine having the above formula.

What I Vclaim is:

1. A method ofl preparing an alicyclic guanamine which comprises dissolving a. biguanide and an ester of an alicyclic carboxylic acid in a 5. A method according to claim 1 in which the reaction takes place in the presence of a. metal alkoxide.

6. A method according to claim 2 in which the reaction takes place in the presence of a. metal alkoxide.

'1. A method according to claim 1 in which a metal alkoxide is present in the reaction in substantially stoichiometrical proportions.

8. A method according to claim 2 in which a metal alkoxide is present in the reaction in substantially stoichiometrical proportions.

JACK THEO THUBJSTON. 

